Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

SAND2018-12184PE

Hydrogen Embrittlement Considerations for

Distribution of Gaseous Hydrogen by Pipeline

Chris San Marchi and Joe Ronevich

Sandia National Laboratories

PRCI mtg, October 2018

Pleasanton CA

SAN D2018-XXXX C
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly
owned subsidiary of Honeywell International, inc., for the U.S. Department of Energys National Nuclear Security Administration under contract DE-NA-0003525
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 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

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Outline and Motivation

Why hydrogen in pipelines?

What is hydrogen embrittlement and when is it important?

How does gaseous hydrogen affect fatigue and fracture of

pipeline steels?

Is there a threshold below which hydrogen effects can be

ignored?

Can the effects of hydrogen be masked by other physics?

 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Hydrogen can be used as an energy carrier

to store and convey energy as well as to serve a wide
range of industrial and transportation applications
Value Added
Applications Current H2 usage in
Electricity the US is about 10
Grid million MT annually,
Hydrogen
mostly for refining
Vehicle and fertilizer
production
Synthetic 0
Fuels 23
-4
Solar PV
U rading t0
Oil/ rz
a

Nuclea
NH3 Close to 1,000 km of
Hydrogen Other Metals
pipeline in the US
Generation End Use Refining are dedicated to
s'c hydrogen coveyance
Concent lar

Illustrative example, not comprehensive; from H2@Scale Concept, developed by FCTO/DOE

 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Hydrogen embrittlement occurs in materials under the

influence of stress in hydrogen environments

Bulk
Environment Hydrogen interactions

\
embrittlement 0 4.\ H
Surface / N"H
interactions
also called H

hydrogen-assisted *silt 4,
fatigue and fracture '
t i
I

Stress / Hydrogen-assisted
HH
Materials fracture
Mechanics AZ`
•24
H
Hy
H

ydro ociates on metal surfaces,

dissolves into the metal lattice, and changes
the mechanical response of the metal
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

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Fracture mechanics-based assessment of
fatigue and fracture of pipelines

Rupture

/ determined by
fracture
resistance

i _____
Evolution of
flaw size
. determined by
Number of pressure cycles, N Nc fatigue crack
growth

ASME B31.12 describes rules for hydrogen pipelines with

reference to ASME BPVC Section VIII, Division 3, Article KD-10
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 Sandia National Laboratories

What are the requirements to use a given

material in gaseous H2 service?

10-5

Fatigue crack growth rate

is accelerated by 10X in
H2 compared to air
Is this material safe to use
in gaseous hydrogen?
Yes - No - Maybe
• heat N
heat N
• heat P Laboratory gas
• heat C
air (heat N) cylinders are made
5 6 7 8 9 10 20 30 40 50 of this material
AK(MPa m112)
 Sandia National Laboratories

What are the requirements to use a given

material in gaseous H2 service?

10-5
Materials requirements
depend on the application
and the design
Gas cylinders are made
from relatively low
strength steels
• Wall stresses are
• heat N relatively low
heat N
• heat P
• heat C Number of pressure
air (heat N)
cycles are modest
5 6 7 8 9 10 20 30 40 50
AK(MPa m112) • Manufacturing defects are
well characterized
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Various pipeline steels tend to show very similar

fatigue crack growth rates in gaseous hydrogen

• A wide variety of
I-. •• R = 0.5
pipeline steels display
nominally the same
fatigue response in
high-pressure gaseous
hydrogen
■ X100A(21 MPa)
• X100A(air) • The effect of pressure
+ )[65(air)
• ][65(21 MPa)
CI X80(21 MPa)
on fatigue crack growth
x X60(21 MPa)
+ ]L10013(21 MPa)
rates is modest for high-
▪ X70A(34 MPa)
A X708(34 MPa) pressure hydrogen
A X52 Vintage(34 MPa) HH
•Z`
yS
▪ X52 Modern (34 MPa)
10-1( 0
5 6 7 8 910 20 30 40 50 H

AK(MPa m112) 54,

HH
HH HH
HH
 Sandia National Laboratories iSFL

Th,effects of H2 on fatigue crack growth in steels

can be captured with "master" design curve
10-2 •
R=0.5
- f =1 Hz
AA
A ''AA
21 MPa H • Tested steels represent:
AAA
t#
A.•
Wide range of strength
Wide range of
microstructure
• A relatively simple master
HH
HH HH

curve has been developed

• X52 (dashed line) that bounds
• X60
• X65 fatigue crack growth
• X80-B performance in gaseous
• X100A
A X100B hydrogen
10-6
5 6 7 8 9 10 20 30 40 50 1/2
da [1 + C2Ri mon f
AK(MPa m112) =
dN 1 1—R Vo)
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

imikTYlpeline steels have relatively high fracture

resistance in gaseous hydrogen
120

Data sets that evaluate

100
effect of pressure on
a_
2 fracture are relatively
80
z limited
0 60 4 Available data suggest
(7)
fracture depends on
2 40I-
cy
—A— X60
X80-B
pressure
—0— X80-E Minimum fracture
C.)
El 20
X80-F resistance per Fracture resistance
u_ Grade B (as rolled)
Grade B (normalized) ASME B31.12 (even at low pressure)
0 I I is significantly lower
0 20 40 60 80 100
Hydrogen test pressure (MPa) than in air
Fro m : San Marchi et al, ASME PVP-2011 conf.
 Sandia National Laboratories

Low pressure H2 has substantial effect on

fracture resistance of pipeline steels
1.2 1 1 1 • Measurements of
fracture resistance in
1
gaseous mixtures of
H2 and N2 show
substantial effects of H2
1% H2 is only modestly
different than 100% H2
PH2 = 0.85 bar
PH2 = 8.5 bar
PH2 = 85 bar _
0.2

1
0
c\J <1 bar of H2 reduces
z
o
0 o
fracture resistance
1
- 0
1-
From: Briottet et al, ASME PVP-2018 conf.
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Low pressure H2 has subItantial effect on

fatigue crack growth of pipeline steels
0.1

: 12 MPa total pressure Measurements in gaseous

••
0.01 '
te,..*:A*.s mixtures of H2 and N2
000••
. 41*,
0,oweib•• show acceleration of
da/(1\ / mm/cycle

1E-3 AA AAA AA fatigue crack growth rate

A
A AA4 with 5% H2
1E-4 N2

• 10vol% H2 *
5vol% H2
20vol% H,
But little additional
R = 0.1 • 50vol% H, acceleration with higher
- 1 Hz
1E-5 H2 content
30 40 50 60 70 80

AK TNIPa rn"

From: Meng et al, IJ Hydrogen Energy 42 Small amounts of hydrogen

(2017)7404.
can have substantial effect
on fatigue and fracture
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Impurities can influence measurements, but can also

provide pathways to mitigate the effects of H2
10-2
X52 Base Metal
21 MPa H2 Oxygen mitigates
f=10 Hz
R=0.1
H2-accelerated
295 K fatigue crack growth
rates at low AK
Attributed to oxygen
-1 ppm 02
10 ppm 02
diffusion to new
100 ppm 02
1000 ppm 02
crack surfaces
1
5 10 20 50
From: Somerday et al, Acta Mater 61
Stress intensity factor range, AK (MPa m1/2)
(2013)6153.

Impurity content in H2 can have substantial effects

on both measurements and in-service performance
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Th, role of mixed hydrogen gas environments

and impurities should be considered carefully
Small partial pressure of gaseous H2 can have substantial
effects on fracture and fatigue of steels
Oxygen can mitigate effects of H2 in ferritic steels
Sensitive to mechanical and environmental variables
Other passivating species can have similar effects
Structural integrity of pipelines carrying mixed gases will
depend sensitively on the details
NG has many impurities, which can mitigate H2 effects
Pure methane is inert and even small additions of H2 can be
significant

Materials compatibility for hydrogen containment structures

depends on the application and the design
 EjSandia National Laboratories ItFCHydrogen and Fuel Cells Program

ilii— NI
SurnmarY

Why hydrogen in pipelines?

Hydrogen is a carbon-free energy carrier
What is hydrogen embrittlement and when is it important?
Hydrogen degrades mechanical properties of most metals
How does gaseous hydrogen affect fatigue and fracture of
pipeline steels?
Fatigue is accelerated by >10x and fracture resistance is
reduced by >50%
Is there a threshold below which hydrogen effects can be
ignored?
NO, even small amounts of hydrogen have large effects
Can the effects of hydrogen be masked by other physics?
Oxygen can mitigate the effects of hydrogen in some cases,
which perhaps can be exploited
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

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Additional slides:
example structural integrity calculations
(see SAND2017-
 Sandia National Laboratories

Consider a typical "high-pressure" pipeline

Material: X70 OD = 762 mm
TS = 586 MPa t = 15.9 mm
YS = 500 MPa Pmax = 7 MPa.
Pmin = 4 MPa
Semi-elliptical crack
A

thickness(t)

inside surface

a/t = crack depth 2c = 3a

a/2c = depth to length ratio A

natural crack shape: a/2c = 1/2 semi-elliptical

ASME crack shape: a/2c = 1/3

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 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Stress intensity associated with semi-

elliptical crack in "high-pressure" pipeline
Hoop stress at P,,,,,„ = 162 MPa
stress ratio: hoop/TS = 28%
50 Minimum KIH -_ Driving force on semi-elliptical
(per ASME B31.12) crack:
,,,-, 40

E
co 30
o_
2
Kir
.< 40 MPa n11/2

Typical pipeline material fracture

1)
'ctl 20
E resistance: o

10
KJH> 75 MPa n11/2
Fracture resistance of pipeline
0 steels in H2 is greater than driving
0 0.2 0.4 0.6 0.8 1
Crack Depth, a/t force on semi-elliptical cracks
 Sandia National Laboratories ItFCHydrogen and Fuel Cells Program

Predicted lifetime of pipeline witrgrowing

fatigue cracks in hydrogen
Time (years) — 2 cycles/day Assuming
8 16 24 32 40 48 56 64 • Pressure cycles between
4 & 7 MPa
0.8
a/2c =1/3 • Constant crack shape (a/2c)
a/2c =1/2 - • Large initial defects
0.6
cp_ • Fatigue crack growth rates in
sa)
a/2c =1/2 pure H2 (at higher pressure)
0 0.4
a=a,
Using:
0 a/2c =1/3 a= a,+(dcy ) N
0.2
dN
• 10,000s of cycles are needed to
1 6,000
1 ' 20,000
1 '30,000
1 '46,0'
00
1 50,000 extend the crack significantly
Number of cycles
• At 2 cycles per day, decades are
needed to advance the crack